Alkanes and Cycloalkanes

Structure Forms
C3H8

Kekul or Wedge/dash

H3C CH2 CH3

skeletal

H H

CH3CH2CH3
condensed

H H H

Classes of Hydrocarbons
Organic Compounds

hydrocarbons (C,H)

heteroatomic (O, N, P, S, X, etc.)

aliphatic (fatty)

aromatic (pleasant smelling)

alkane C C

alkene C C

alkyne C C

cyclic

Functional Groups
 

A functional group is an atom or group of atoms that have a characteristic chemical behavior. The chemistry of every organic molecule, regardless of size and complexity, is determined by the functional groups it contains.

Functional Groups

O C H3 C O O C O
5

Types of Functional Groups: Multiple CarbonCarbon Bonds

  

Alkenes have a C-C double bond Alkynes have a C-C triple bond Arenes have special bonds that are represented as alternating single and double C-C bonds in a sixmembered ring
6

Functional Groups


Alkyl halide
H H C H H C H H C H H C H Br

R-X where X is any halogen X

7

Functional Groups


Alcohols
H H C H H C H H C H H C H OH

R-OH where R is any alkyl group

8

Functional Groups


Ethers
H H C H H C H H O C H H

R-O-R where R is any alkyl group

9

Functional Groups


Aldehydes

H O H C H
10

C H

Functional Groups


Ketone

H O H H C C C H

H H Propanone (acetone)
11

Functional Groups


Carboxylic acids

H O H C H
Ethanoic acid (acetic acid)
12

C OH

Functional Groups


Ester

H H C H

O C O CH3

Methyl ethanoate (methyl acetate)

13

Functional Groups


Amine

H H C H
Methylamine

NH2

14

Functional Groups


Amide

O H3 C C NH2
Ethanamide (acetamide)
15

Functional Groups


Acid anhydride

O H3 C

O CH3

C O C

Ethanoic anhydride
16

Functional Groups


Acid halide

O H3 C C Cl
Ethanoyl chloride
17

Functional Groups


Nitro

O H3 C N O
18

Nitromethane

Functional Groups


Arene

benzene
19

Functional Groups


Halide

H3 C

Cl

Chloromethane
20

Functional Groups


Nitrile

H3 C

C N

Ethanenitrile

21

Functional Groups


Sulfide

H3 C

CH3

22

Functional Groups


Thiol

H3 C

Methanethiol

23

Functional Groups
O OCH3 O N H HO O
24

NH2

Alkanes and Alkane Isomers

    

Alkanes: Compounds with C-C single bonds and C-H bonds only (no functional groups) Connecting carbons can lead to large or small molecules The formula for an alkane with no rings in it must be CnH2n+2 where the number of Cs is n Alkanes are saturated with hydrogen (no more can be added They are also called aliphatic compounds

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Alkanes
H3C CH2 CH2 CH3 H H H H H C C C C H H H H H CH3CH2CH2CH3 H C H H C H H CH3(CH2)2CH3

H H C H

H C H

CH3CH(CH3)CH2CH3
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Structure


Shape
 

tetrahedral about carbon all bond angles are approximately 109.5

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Alkane Isomers
 

CH4 = methane, C2H6 = ethane, C3H8= propane The molecular formula of an alkane with more than three carbons can give more than one structure  C4 (butane) = butane and isobutane  C5 (pentane) = pentane, 2-methylbutane, and 2,2dimethylpropane Alkanes with Cs connected to no more than 2 other Cs are straight-chain or normal alkanes Alkanes with one or more Cs connected to 3 or 4 Cs are branched-chain alkanes

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Alkanes


straight chain or normal alkanes

H H H H C C H H H H H H H C C C H H H H H H H H H C C C C H H H H H

H C H H

29

Alkanes


branched chains

H H H H H H H H C C C C C H H H H H H H C H H H H H C C C C H H H H H H C H H H H C C C H H H H C H H
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Branching vs. No Branching



There are 2 isomeric butanes



n-butane


H H C H

H C H

H C H

H C H H

C4H10

n means normal or in a straight chain

H H H H C H C C H H H C H H
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isobutane


C4H10

Find the Isomers of C5H12

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Find the Isomers of C6H14

Draw the structures for C6H14 starting with the longest chain (6 in a row) H H H H H H
H C H C H C H C H C H C H H

next draw all structures with 5 carbons in the longest chain (substitute for the H s)
then substitute for other H s
H H C H H H H C C C H H H H C H H C H H
33

Find the Isomers of C6H14

34

Find the Isomers of C7H16

35

Isomers


Same chemical formula, but different structure.

36

Constitutional Isomers
  

Isomers that differ in how their atoms are arranged in chains are called constitutional isomers Compounds other than alkanes can be constitutional isomers of one another They must have the same molecular formula to be isomers

37

Constitutional Isomerism
Molecular Cons titutional Formula Isomers CH 4 C 5 H12 C 10 H22 C 15 H32 C 30 H62 1 3 75 4,347 4,111,846,763
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World population is about 6,000,000,000

Names of Small Hydrocarbons

No. of Carbons 1 2 3 4 5 6 7 8 9 10 Formula Name Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane (CnH2n+2) CH4 C 2H 6 C 3H 8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22
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Alkyl Groups
  

Alkyl group remove one H from an alkane (a part of a structure) General abbreviation R (for Radical, an incomplete species or the rest of the molecule) Name: replace -ane ending of alkane with -yl ending
 

CH3 is methyl (from methane) CH2CH3 is ethyl from ethane

See Table 3.4 for a list

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Types of Alkyl groups



Classified by the connection site (See Figure 3.3)  a carbon with one carbon attached to it (primary alkyl group)  a carbon with two carbons attached to it (secondary alkyl group)  a carbon with three carbons attached to it (tertiary alkyl group)  a carbon with four carbons attached to it (quaternary alkyl group)

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Types of Alkyl groups



Classified by the connection site (See Figure 3.3)

   

a carbon with one carbon attached to it (primary alkyl group) a carbon with two carbons attached to it (secondary alkyl group) a carbon with three carbons attached to it (tertiary alkyl group) a carbon with four carbons attached to it (quaternary alkyl group)

CH3

CH3 CH3 CH3 C CH2CH C CH3 CH3 CH3

42

Degree of Substitution

CH3
1 3

4 CH 3

CH3CHCHCH2CH2C CH3 CH2 CH3 CH3

43

Nomenclature

International Union of Pure and Applied Chemistry

colloquially: eye-you-pac

Devised following WWII ca. 1946-1950

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Naming Alkanes


Compounds are given systematic names by a process that uses



Prefix-Parent-Suffix Named as longest possible chain Carbons in that chain are numbered in sequence substituents are numbered at their point of attachment Compound name is one word (German style) Complex substituents are named as compounds would be

Follows specific rules

    

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Nomenclature Where are substituents? Prefix-Parent-Suffix

How many carbons? What family?

International Union of Pure and Applied Chemistry (IUPAC)
46

Nomenclature Prefix-Parent-Suffix

CH3 CH2 CH CH2 CH2 CH CH2 CH3 CH3

3-ethyl-6-methyl

CH2 CH3

octane
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Nomenclature
Name Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane

Alkanes have the general formula CnH2n+2

Condensed Structure CH4 CH3CH3 CH3CH2CH3 CH3(CH2)2CH3 CH3(CH2)3CH3 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 CH3(CH2)9CH3 CH3(CH2)10CH3

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The Longest Continuous Chain of Carbon Atoms

C-C C -C -C -C -C -C -C -C -C C
all possibilites must be examined it wont always be the horizontal one as shown here

try these also ..

C -C C- C-C-C -C-C-C-C-C C C

C -C C-C-C- C-C-C-C-C-C

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Nomenclature


Parent name of the longest carbon chain is alkane  Groups attached to the parent chain are called substituents Each substituent is given a name and a number


If substituent occurs more than once, di-, tri-, tetra-, etc.

50

Nomenclature


Number the chain to give the substituent encountered first the lowest number If there are different substituents, list them in alphabetical order. The following are not included in alphabetization.
 

di-, tri-, tetra-, etc. hyphenated prefixes, such as sec- and tert-

51

Nomenclature


Alkyl groups
     

Propyl Isopropyl Butyl Isobutyl sec-butyl tert-butyl

-CH2CH2CH3 -CHCH(CH3)2 -CH2CH2CH2CH3 -CH2CHCH(CH3)2 -CH(CH3)CH2CH3 -C(CH3)3

52

Nomenclature


Alkyl groups
Name pentyl isopentyl Condens ed Structural Formula -CH 2 CH2 CH 2 CH 2 CH 3 -CH 2 CH2 CHCH3 CH 3 CH3 neopentyl -CH 2 CCH 3 CH3
53

Nomenclature


Find the longest chain.

CH 2 CH 3 CH3CH2CH2CH CH3
CH3 CH2 H3C CH CH CH2CH 3 CH2CH 2CH3

hexane

heptane

54

Nomenclature


If two different chains of equal length are present, choose the one with the larger number of branch points.

CH3 CH3CHCHCH2CH2CH3 CH2 CH3

55

Nomenclature


Number the atoms in the main chain:



Begin at the end nearer the first branch point (lower number).
1 2

CH3 CH2
3 4

H 3C

CH CH CH2 CH3 CH2 CH2 CH3

5 6 7
56

Nomenclature


If branching is equal distant away from both ends of the parent chain, begin at the end nearer the second branch point.

H3C CH2 CH3 CH3CHCH 2CH2CHCHCH2CH3 CH2 CH3

57

Nomenclature


Identify the number of substituents:



Assign a number to each substituent according to its point of attachment to the main chain.

3-ethyl 9 8 4-methyl H3C CH2 CH3 3 7-methyl CH3CHCH2CH2CHCHCH2CH3 7 6 5 4 CH2 CH3 2 1

3-ethyl-4,7-dimethylnonane

58

Nomenclature


If there are two substituents on the same carbon, assign them both the same number.

4-ethyl-2,4-dimethylhexane

CH3 CH3 CH3CH2CCH2CHCH3 CH2 CH3

2-methyl 4-methyl 4-ethyl

59

Nomenclature


 

Write the name as a single word, using hyphens to separate the different prefixes and commas, to separate numbers. Use di-, tri-, etc. if more than one identical substituents Dont use these prefixes for alphabetizing purposes.

60

Nomenclature
3-methylhexane

CH2 CH3 CH3CH2CH2CH CH3

61

Nomenclature
4-ethyl-3-methylheptane

1 CH33 CH 2 CH2 CH 2 4 CH3CHCHCH2CH3 CH 33 CHCHCH 2CH 3 CH2 CH2 CH3 CH 2 CH2 CH 3 6 7 5

62

Nomenclature
3-ethyl-2-methylhexane

CH3 CH3CHCHCH2CH2CH3 CH2 CH3

63

Nomenclature


Name a complex substituent and begin numbering at the point of attachment and set it off in parentheses.

CH3 CH3CH CHCH2CH2CH CH2CH CH3 CH3 CH3 CH2CH2CH2CH3

64

Nomenclature
2,3-dimethyl-6-(2-methylpropyl)decane 2-methylpropyl CH3 1
CH3CH CHCH2CH2CH CH2CH CH3 CH3 CH3 CH2CH2CH2CH3
65

CH 3 CH 3

Nomenclature

CH CHCH 3

1,2-dimethylpropyl

CH 3 CH3 CH 3CH 2CH2CH2CH CH CHCH3 CH 2 CH 3 CH 2 CH CH 3

2-methyl-5-(1,2-dimethylpropyl)nonane
66

Nomenclature-Historical


Threecarbon alkyl group:

CHCH3


isopropyl (i-pr)

CH3
67

Nomenclature-Historical


Fourcarbon groups:

CHCH2CH3 CH3

CH2CHCH3 CH3

CH3 C CH3 CH3

sec-butyl

isobutyl

tert-butyl

68

Nomenclature-Historical


Fivecarbon alkyl groups:

CH2CH2CHCH3 CH3
isopentyl

CH3 CH2CCH3 CH3

neopentyl
69

Nomenclature

H 3C CH CH3 H3C CH2 CH 2 CH CH2 CH2CH 3

4-(1-methylethyl)heptane or 4-isopropylheptane

70

If you can name this, you can name anything!

CH3
1 2 3 4 5 6

CH3 CH3

CH3 CH CH2 CH CH2 C CH3 CH 7 CH3 8

9

CH2 CH2 CH3

71

4-isopropyl-2,6,6-trimethylnonane

How about this?

CH3

CH3CH2
2-cyclobutyl-5-methylhexane not (1,4-dimethylpentyl)cyclobutane

CH3

CH3

5-ethyl-1,1,3-trimethyl-2-(2methylpentyl)cyclohexane
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Properties of Alkanes
  

Called paraffins (low affinity compounds) because they do not react as most chemicals They will burn in a flame, producing carbon dioxide, water, and heat They react with Cl2 in the presence of light to replace Hs with Cls (not controlled)

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Physical Properties
 

Boiling points and melting points increase as size of alkane increases Forces between molecules (temporary dipoles, dispersion) are weak

74

Alkane MP & BP Trends



The dependence of the boiling and melting points on chain length can be explained in terms of increasing attractive van der Waals interactions as the chain length increases.

75

Cycloalkanes
  

Cycloalkanes are alkanes that have carbon atoms that form a ring (called alicyclic compounds) Simple cycloalkanes rings of CH2 units, (CH2)n, or CnH2n Structure is shown as a regular polygon with the number of vertices equal to the number of Cs (a projection of the actual structure)

cyclobutane cyclopropane cyclopentane cyclohexane

76

Cycloalkanes

77

Cycloalkanes
CH2OH CO H3C OH H O H
cortisone
78

O H3C

Cycloalkanes


Structure and nomenclature



  

to name, prefix the name of the corresponding openchain alkane with cyclo-, and name each substituent on the ring if only one substituent, no need to give it a number if two or more substituents, number from the substituent of lowest alphabetical order where there is choice, number to give substituents the lowest set of numbers

79

Naming Cycloalkanes


Count the number of carbon atoms in the ring and the number in the largest substituent chain. If the number of carbon atoms in the ring is equal to or greater than the number in the substituent, the compound is named as an alkyl-substituted cycloalkane For an alkyl- or halo-substituted cycloalkane, start at a point of attachment as C1 and number the substituents on the ring so that the second substituent has as low a number as possible. Number the substituents and write the name


if only one substituent, no need to give it a number

See text for more details and examples

80

Nomenclature


For alkyl-substituted cycloalkanes, start at the point of attachment and number the substituents on the ring so as to arrive at the lowest sum.
CH 3
1 6 5 4 2 3

1,3-dimethylcyclohexane not 1,5-dimethylcyclohexane

CH 3
81

Nomenclature


Halogens are treated exactly like alkyl groups.

1-bromo-3-ethyl-5-methylcyclohexane Br CH3
3 4 2 1

Br

CH3CH2

CH 3
82

1-bromo-2-methylcyclobutane

Cis-Trans Isomerism in Cycloalkanes

  

Rotation about C-C bonds in cycloalkanes is limited by the ring structure Rings have two faces and substituents are labeled as to their relative facial positions There are two different 1,2-dimethyl-cyclopropane isomers, one with the two methyls on the same side (cis) of the ring and one with the methyls on opposite sides (trans)

83

Stereoisomers
  

Compounds with atoms connected in the same order but which differ in three-dimensional orientation, are stereoisomers The terms cis and trans should be used to specify stereoisomeric ring structures Recall that constitutional isomers have atoms connected in different order

84

Cis-Trans Isomerism
H3 C CH3

H3 C CH3

cis-1,2-dimethylcyclopropane trans-1,2- dimethylcyclopropane

85

Cis-trans isomerism


1,2-dimethylcyclopentane

H H H

H H H

H H H

H CH3 H

H CH3 CH3 cis-1,2-dimethylcyclopentane

CH3 H trans-1,2-dimethylcyclopentane

86

Cis-trans isomerism


1,4-Dimethylcyclohexane


planar hexagon representations

H CH3 H H

H H3 C trans -1,4-Dimethylcyclohexane

H3 C CH3 cis -1,4-Dimethylcyclohexane

87